EP0452840A2 - Copolymère syndiotactique de propylène, préparation et composition de résine contenant ce copolymère - Google Patents

Copolymère syndiotactique de propylène, préparation et composition de résine contenant ce copolymère Download PDF

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Publication number
EP0452840A2
EP0452840A2 EP91105945A EP91105945A EP0452840A2 EP 0452840 A2 EP0452840 A2 EP 0452840A2 EP 91105945 A EP91105945 A EP 91105945A EP 91105945 A EP91105945 A EP 91105945A EP 0452840 A2 EP0452840 A2 EP 0452840A2
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Prior art keywords
propylene
formula
copolymer
carbon atoms
units
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EP91105945A
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German (de)
English (en)
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EP0452840B1 (fr
EP0452840A3 (en
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Tadashi Asanuma
Hiroshi Matsuzawa
Tateyo Sasaki
Kaoru Kawanishi
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Mitsui Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the present invention relates to propylene copolymers having a syndiotactic structure, preparation of the same and resin compositions containing the same. More particularly, it relates to propylene copolymers having -OH group in the side chain, which copolymers have high syndiotacticity, processes for producing the syndiotactic propylene copolymers and resin compositions containing one or more of the copolymers.
  • Polyolefins are low-priced and have relatively excellent physical properties. However, as having no polar group, they have some problems that the gas-barrier property is poor and the adhesiveness to polar group-having polymers is poor. In order to overcome the problems, a polar group-having polymer may be added to such a polyolefin. However, in general, the addition of such a polymer involves another problem that polar group-having polymers could hardly be blended with polyolefins and the resulting blend would often lose the physical properties inherent in polyolefins.
  • syndiotactic polypropylene has been known for many years.
  • polypropylene obtained by a conventional low-temperature polymerization method of using a catalyst comprising a vanadium compound, ether and an organoaluminium compound has poor syndiotacticity so that it can hardly be considered to have the characteristic properties as syndiotactic polypropylene.
  • olefin polymerization catalysts are used, olefins having polar groups such as - OH are not almost polymerized. Under the situation, polar group-having stereoregular polyolefins have heretofore been unknown.
  • Copolymers having a substantially syndiotactic structure and having -OH group in the side chain have heretofore been unknown. Such copolymers are expected to have physical properties which could not be seen in any conventional copolymers, and compositions containing such copolymers are also expected to have physical properties which could not be seen in any conventional compositions.
  • An object of the present invention is to provide a novel propylene copolymer having -OH group in the side chain and having a substantially syndiotactic structure.
  • Another object of the present invention is to provide a method of producing the novel propylene copolymer.
  • Still another object of the present invention is to provide a resin composition which contains the novel propylene polymer and which has excellent physical properties.
  • a syndiotactic propylene copolymer having -OH group in the side chain which comprises repeating units of the formula (I): and from 0.01 to 40 mol% of repeating units of the formula (II): where n represents 0 or an integer of 1 or more, wherein, of absorption peaks attributed to the methyl groups of the propylene units on an absorption spectrum by 13C-NMR, the intensity of an absorption peak observed at about 20.2 ppm is 0.3 or more of the intensity of absorption peaks of all the methyl groups attributed to the propylene units.
  • the propylene copolymer having -OH group in the side chain means a polymer merely comprising repeating units of propylene and repeating units having -OH group in the side chain.
  • polyolefin resin composition comprising the above-mentioned propylene copolymer and other polyolefin(s).
  • the catalyst systems described in the above-mentioned J.A. Ewen et al literature are referred to.
  • other catalyst systems having a different structure may also be used provided that, when a propylene homopolymer is produced in the presence of a catalyst system containing them, the homopolymer could be one having such good tacticity as being about 7.0 or more in terms of syndiotactic pentad fraction (A. Zambelli et al., Macromolecules, Vol. 6, 925(1973); ibid., Vol. 8, 687 (1975)).
  • examples of A and B include monocyclic or polycyclic unsaturated hydrocarbon residues each having from 5 to 30 carbon atoms. Specific examples of them include monocyclic unsaturated hydrocarbon residues, such as a cyclopentadienyl group or a substituted cyclopentadienyl group in which a part or all of hydrogen atoms is/are substituted by (an) alkyl group(s) each having from 1 to 10 carbon atoms (where the alkyl moiety may have a structure of being bonded to the cyclopentadiene ring at the terminal thereof), as well as polycyclic unsaturated hydrocarbon residues, such as an indenyl or fluorenyl group or a substituted indenyl or fluorenyl group in which a part or all of hydrogen atoms is/are substituted by (an) alkyl group(s) each having from 1 to 10 carbon atoms.
  • monocyclic unsaturated hydrocarbon residues such as a cyclopentadieny
  • R3 preferred are a dialkylmethylene group, a dialkylsilylene group and a dialkylgerylene group.
  • R3 groups of R42C ⁇ , R42Si ⁇ and R42Ge ⁇ (where R4's may be same as or different from each other and each represents a hydrogen atom or an alkyl group having from 1 to 20 carbon atoms).
  • R4 an ethylidene group of -CR42-CR42- (where R4 has the same meaning as mentioned above).
  • X there are mentioned fluorine, chlorine, bromine or iodine atom, and an alkyl group such as a methyl, ethyl, propyl or butyl group, and a cyclic unsaturated hydrocarbon residue such as a cyclopentadienyl group. Above all, especially preferred is a chlorine atom or a methyl group.
  • transition metal compounds having asymmetrically interconnected ligands preferred are isopropyl(cyclopentadienyl-1-fluorenyl) hafnium dichloride and isopropyl(cyclopentadienyl-1-fluorenyl) zirconium dichloride as well as compounds derived from them by partly substituting hydrogens by (an) alkyl group(s), as described in the above-mentioned J. A. Ewen et al literature.
  • purified ones having a high purity are preferred as giving copolymers having a much higher stereoregularity.
  • the compounds of the formula (VI): where R5 represents a hydrocarbon residue having from 1 to 3 carbon atoms, and m represents an integer of from 1 to 50, and the formula (VII): where R5 and m have the same meanings as mentioned above, are preferred.
  • R5 is a methyl group and m is 5 or more.
  • the proportion of the aluminoxane to the above transition metal compound in the catalyst system of the invention may be from 1/1 to 1000000/1 by mol, especially preferably from 10/1 to 5000/1 by mol.
  • alkenylsilane of the formula (III) to be copolymerized with propylene examples include vinylsilane, allylsilane, butenylsilane, pentenylsilane and hexenylsilane, as well as compounds to be derived from such silanes by substituting from 1 to 3 hydrogens by (a) halogen atom(s) or especially by (a) saturated hydrocarbon residue(s) each having from 1 to 20 carbon atoms.
  • alkenylborane compound to be copolymerized with propylene examples include compounds of formula (IV) where R2 is an alkyl group such as a methyl, ethyl, propyl, butyl, pentyl or hexyl group, compounds of formula (IV) where two alkyl groups of R2s are bonded to each other, and compounds of formula (IV) where R2 is a cyclic group, such as B-7-octenyl-9-borabicyclo[3,3,1]nonane.
  • the method of copolymerizing propylene and the above-mentioned alkenylsilane or alkenylborane compound is not specifically defined but any of a solvent polymerization method of using an inert medium, a bulk polymerization method of effecting polymerization substantially in the absence of a solvent and a gaseous polymerization method may be employed.
  • the polymerization temperature is preferably within the range between -100°C and 200°C, especially preferably between -100°C and 100°C; and the polymerization pressure is preferably from atmospheric pressure to 100 kg/cm2 (gauge pressure), especially preferably from atmospheric pressure to 50 kg/cm2 (gauge pressure).
  • the amount of the above-mentioned alkenylsilane or alkenylborane compound to be copolymerized is so controlled that the proportion of the repeating units of the above-mentioned formula (II) may be from 0.01 to 40 mol%, preferably from 0.05 to 20 mol%, especially preferably from 0.1 to 20 mol%, to the resulting copolymer.
  • the propylene-alkenylsilane copolymer obtained is then heat-treated in the presence of a trialkylamine oxide and KF ⁇ HF, whereby -SiR13 group in the copolymer is converted to -OH group.
  • a trialkylamine oxide and KF ⁇ HF for example, those illustrated in Tetrahedron Letter, 27 , 75 (1986) are referred to.
  • the trialkylamine oxide one having alkyl groups each with approximately from 1 to 6 carbon atoms may be used, and the amount of the compound to be used may be from 0.01 to 1000 molar times, preferably from 0.1 to 100 molar times, to the alkenylsilane units in the copolymer to be heat-treated.
  • the amount of KF ⁇ HF to be used may be from 0.01 to 1000 molar times, preferably from 0.1 to 100 molar times, to the alkenylsilane units.
  • the reaction is preferably carried out in the presence of a solvent, and a hydrocarbon compound having from 5 to 25 carbon atoms is preferably used as a solvent.
  • the reaction temperature is generally from room temperature to 300°C, especially preferably from 50°C to 200°C.
  • the propylene-alkenylborane copolymer obtained is then oxidized and decomposed.
  • the condition for oxidation and decomposition is not specifically defined but any condition employable for decomposing an alkylboron to give an alcohol may directly apply to the step.
  • the copolymer may be treated with an oxidizing agent such as hydrogen peroxide under an alkaline condition whereby -BR22 group in the copolymer may easily be decomposed to -OH group.
  • the intensity of an absorption peak observed at about 20.2 ppm is 0.3 or more of the intensity of absorption peaks of all the methyl groups attributed to the propylene units. If the ratio is less than 0.3, there would be a problem that the surface of the shaped article from the copolymer is often tacky.
  • the copolymer could not display the effect resulting from the existence of -OH groups therein even though all the alkenylsilane units or alkenylborane units are converted into -OH groups. On the contrary, however, if it is more than 40 mol%, the copolymer could not display physical properties as a syndiotactic polypropylene.
  • the copolymer has an intrinsic viscosity of 0.05 or more, generally approximately from 0.1 to 10, as measured at 135°C in the form of a tetralin solution, in view of the easy use of the copolymer.
  • the ratio of the weight-average molecular weight to the number-average molecular weight of the above-mentioned copolymer as measured at 135°C in the form of a 1,2,4-trichlorobenzene solution is not specifically defined but may fall within the range between 1.5 to 20, as it depends upon the polymerization condition.
  • the preferred range may suitably be selected in accordance with the use of the copolymer.
  • the ratio may fall within the range between 2 and 10 or so.
  • hydrocarbon solvents usable for the purpose are those having from 3 to 20 carbon atoms.
  • propylene, and saturated hydrocarbon compounds such as propane, butane, pentane, hexane, heptane, octane and nonane, as well as aromatic hydrocarbon compounds such as benzene, toluene, xylene and ethylbenzene, and compounds to be derived from them by substituting a part or all of hydrogens by fluorine, chlorine, bromine and/or iodine atom(s).
  • alcohols having from 1 to 20 carbon atoms as well as ethers and esters each having from 2 to 20 carbon atoms, which may dissolve or disperse low molecular atactic components, are also usable as the solvent.
  • the washing method is not specifically defined and it may be effected generally at a temperature of 0°C to 100°C.
  • the copolymer of the present invention may be blended with polyolefins so as to improve the physical properties of the copolymer and is used as a resin composition.
  • propylene (co)polymers As polyolefins to be blended with the copolymer of the present invention to form a resin composition of the invention, preferred are propylene (co)polymers.
  • the propylene (co)polymers usable for the purpose include isotactic polypropylenes available in the market (including not only propylene homopolymers but also propylene random or block copolymers with ethylene or an alpha-olefin having from 4 to 12 carbon atoms) as well as syndiotactic polypropylenes to be obtained by homopolymerization of propylene or by copolymerization of propylene with ethylene or an alpha-olefin having from 4 to 12 carbon atoms in the presence of the above-mentioned catalyst.
  • the polyolefins to be blended with the copolymer of the present invention are not specifically defined with respect to the molecular weight thereof, but anyone having a melt flow index as measured at 230°C of being approximately from 0.1 to 100 can be employed.
  • the proportion of the copolymer of the present invention to the other polyolefin(s) to be blended is generally so controlled that the content of the alkenyl alcohol units in the resulting resin composition may fall within the range of from 0.01 to 10 % by weight.
  • it is so controlled that the content of the copolymer of the invention in the resulting resin composition is to fall within the range of from 0.1 to 100 % by weight, especially preferably from 1 to 50 % by weight.
  • the blending method is not specifically defined.
  • the components may well be dry-blended in an ordinary Henschel mixer and then melt-granulated. Needless to say, it is possible to add various known additives such as stabilizer, nucleating agent and the like, to the resin composition of the present invention.
  • Isopropylcyclopentadienyl-1-fluorene which had been synthesized in a manner known per se in the art was converted to the lithium salt.
  • the lithium salt was reacted with zirconium tetrachloride, followed by purification to obtain isopropyl(cyclopentadienyl-1-fluorenyl)zirconium dichloride.
  • the powder thus obtained was washed four times each with 1 liter of methanol and dried at 80°C under reduced pressure to obtain 26 g of a polymer.
  • the polymer was verified to contain 8.5 % by weight of trimethylallylsilane.
  • Fig. 2 shows an infrared absorption spectrum of the polymer.
  • Fig. 1 shows an infrared absorption spectrum of the polymer, in which absorptions of -OH groups (about 2.1 % by weight) were observed at 3400 cm-1 and 1040 cm-1.
  • the intensity of an absorption peak as measured at about 20.2 ppm was 0.69 of the intensity of absorption peaks to be attributed to all the methyl groups of the propylene units.
  • the polymer had an intrinsic viscosity (hereinafter referred to as " ⁇ ") as measured at 135°C in the form of a tetralin solution of being 0.47.
  • Example 2 The same process as in Example 1 was repeated to obtain 24 g of a copolymer, except that trimethylvinylsilane was used in place of allyltrimethylsilane.
  • the copolymer thus produced contained 6.5 % by weight of trimethylvinylsilane, and this was treated in the same manner as in Example 1 to obtain a copolymer containing 4.1 % by weight of trimethylvinylsilane units and having -OH groups (about 1.1 % by weight).
  • the copolymer had ⁇ of 0.64 and MW/MN of 2.1.
  • 13C-NMR of the copolymer the intensity of an absorption peak as measured at about 20.2 ppm was 0.72 of the intensity of absorption peaks to be attributed to all the methyl groups of the propylene units.
  • the polymer thus obtained contained B-7-octenyl-9-borabicyclo[3,3,1]nonane and contained -OH groups (about 5.7 mol%).
  • Fig. 3 shows an infrared absorption spectrum of the polymer; and
  • Fig. 4 shows a 13C-NMR absorption spectrum thereof.
  • the intensity of an absorption peak as measured at about 20.2 ppm was 0.68 of the intensity of absorption peaks to be attributed to all the methyl groups of the propylene units.
  • the copolymer had ⁇ of 0.45 as measured at 135°C in the form of a tetralin solution and had a ratio of the weight-average molecular weight to the number-average molecular weight (MW/MN) of being 2.5 as measured at 135°C in the form of a 1,2,4-trichlorobenzene solution.
  • Example 2 0.2 g of the isopropyl(cyclopentadienyl-1-fluorenyl)zirconium dichloride as obtained in Example 1 and 30 g of methylaluminoxane were dissolved in 80 liters of toluene, and the resulting solution was charged into an autoclave having an internal capacity of 200 liters. Propylene was introduced into the autoclave under polymerization pressure of 3 kg/cm2-G, and polymerization was carried out at 20°C for 2 hours. Methanol and methyl acetacetate were added to the thus obtained polymer mixture, which was treated at 30°C.
  • the polypropylene had a syndiotactic pentad fraction of 0.935. It had ⁇ of 1.45 and MW/MN of 2.2.
  • Example 3 To 100 parts by weight of the polypropylene were added 5 parts by weight of the copolymer as obtained in Example 3 and 0.1 part by weight of a phenolic stabilizer, and the resulting blend was granulated through an extruder and then melt-pressed at 200°C to form a 1 mm thick sheet. The following physical properties of the sheet were measured.
  • the sheet had 5100 kg/cm2 flexural stiffness, 220 kg/cm2 tensile yield strength, 540 % elongation at breakage, 13.8 and 3.5 kg.cm/cm Izod impact strengths (at 23°C and -10°C, respectively), and 29 % haze.
  • the sheet was brush-coated with an acrylic coating composition Unirock (product by Rock Paint Co.) and baked and dried in an air oven at 60°C for 30 minutes.
  • the test piece was subjected to a cross-cut tape-peeling test (JIS K-5400). As a result of the test, the number of the coated film squares as remained after the test was 90 and the adhesion strength of the coated film was good. As opposed to the case, the sheet formed from a copolymer-free homopolypropylene gave the number of being 0 (zero).
  • a 0.5 mm thick press sheet was produced from the copolymer obtained in Example 3.
  • the oxygen gas-permeability of the sheet was measured to be 100 ml/m2 ⁇ atm ⁇ 24hr.
  • the oxygen gas-permeability of the syndiotactic polypropylene as obtained in Example 4 was also measured for comparison, which was 800 ml/m2 ⁇ atm ⁇ 24hr.
  • the shaped article (press sheet) as produced from the copolymer of the present invention has an excellent gas-barrier property.
  • the copolymer of the present invention has improved characteristics of high adhesiveness, coatability and gas-barrier property because of introduction of olefin units having -OH groups, with still having the excellent characteristics of high transparency and impact strength owing to the syndiotactic polypropylene structure of itself. Accordingly, the copolymer of the present invention is an extremely useful copolymer as having an excellent transparency and high stiffness and impact resistance and also having other various excellent functions.
  • the resin composition comprising the copolymer and other polyolefin(s) may give a shaped article having good and well-balanced physical properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
EP91105945A 1990-04-18 1991-04-14 Copolymère syndiotactique de propylène, préparation et composition de résine contenant ce copolymère Expired - Lifetime EP0452840B1 (fr)

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Application Number Priority Date Filing Date Title
JP100386/90 1990-04-18
JP10038690 1990-04-18
JP189378/90 1990-07-19
JP18937890 1990-07-19
JP323140/90 1990-11-28
JP32314090 1990-11-28

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EP0452840A2 true EP0452840A2 (fr) 1991-10-23
EP0452840A3 EP0452840A3 (en) 1991-12-11
EP0452840B1 EP0452840B1 (fr) 1998-10-28

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US (1) US5534595A (fr)
EP (1) EP0452840B1 (fr)
KR (1) KR930011667B1 (fr)
CA (1) CA2040480C (fr)
DE (1) DE69130403T2 (fr)

Cited By (2)

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WO1997041158A1 (fr) * 1996-04-30 1997-11-06 Basf Aktiengesellschaft Cires metallocene-polyolefine oxydees
EP1256593A1 (fr) * 2001-05-11 2002-11-13 Borealis Technology Oy Procédé de réticulation d'articles polymères

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CA2228551A1 (fr) * 1995-09-18 1997-03-27 Exxon Chemical Patents, Inc. Compositions de polypropylene hautement impermeables et leur utilisation comme emballages
US6166161A (en) * 1996-06-24 2000-12-26 The Dow Chemical Company Incorporation of functionalized comonomers in polyolefins
WO2001055231A1 (fr) 2000-01-26 2001-08-02 Mitsui Chemicals, Inc. Polymeres olefiniques et leurs procedes de production
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
KR101113341B1 (ko) 2002-10-15 2012-09-27 엑손모빌 케미칼 패턴츠 인코포레이티드 올레핀 중합용 다중 촉매 시스템 및 이로부터 제조된중합체
CN100402569C (zh) * 2003-02-21 2008-07-16 三菱化学株式会社 聚丙烯共聚物、含有该聚丙烯共聚物的组合物以及生产该聚丙烯共聚物的方法

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EP0351392A2 (fr) * 1988-07-15 1990-01-17 Fina Technology, Inc. Procédé et catalyseur pour produire des polyoléfines syndiotactiques

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Publication number Priority date Publication date Assignee Title
WO1997041158A1 (fr) * 1996-04-30 1997-11-06 Basf Aktiengesellschaft Cires metallocene-polyolefine oxydees
US6348547B1 (en) 1996-04-30 2002-02-19 Basf Aktiengesellschaft Oxidized metallocene-polyolefin waxes
EP1256593A1 (fr) * 2001-05-11 2002-11-13 Borealis Technology Oy Procédé de réticulation d'articles polymères
WO2002096962A1 (fr) * 2001-05-11 2002-12-05 Borealis Technology Oy Procede de reticulation d'un article polymere

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EP0452840B1 (fr) 1998-10-28
US5534595A (en) 1996-07-09
CA2040480C (fr) 1996-11-12
EP0452840A3 (en) 1991-12-11
KR910018422A (ko) 1991-11-30
DE69130403D1 (de) 1998-12-03
DE69130403T2 (de) 1999-04-15
CA2040480A1 (fr) 1991-10-19
KR930011667B1 (ko) 1993-12-16

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